Cu-based catalysts have been widely applied in electroreduction of carbon dioxide (CO 2 ER) to produce multicarbon (C 2 + ) feedstocks (e.g., C 2 H 4 ). However, the high energy barriers for CO 2 activation on the Cu surface is a challenge for a high catalytic efficiency and product selectivity. Herein, we developed an in situ *CO generation and spillover strategy by engineering single Ni atoms on a pyridinic N-enriched carbon support with a sodalite (SOD) topology (Ni-SOD/NC) that acted as a donor to feed adjacent Cu nanoparticles (NPs) with *CO intermediate. As a result, a high C 2 H 4 selectivity of 62.5 % and an industrial-level current density of 160 mA cm À 2 at a low potential of À 0.72 V were achieved. Our studies revealed that the isolated NiN 3 active sites with adjacent pyridinic N species facilitated the *CO desorption and the massive *CO intermediate released from Ni-SOD/NC then overflowed to Cu NPs surface to enrich the *CO coverage for improving the selectivity of CO 2 ER to C 2 H 4 .

Improving the proton transfer rate in proton-coupled electron transfer process is the key to accelerating the reaction kinetics of CO2 electroreduction (CO2ER). However, the synchronous enhancing proton feeding and activating...

Electrosynthesis of H2O2 has great potential for directly converting O2 into disinfectant, yet it is still a big challenge to develop effective electrocatalysts for medical‐level H2O2 production. Herein, we report the design and fabrication of electrocatalysts with biomimetic active centers, consisting of single atomic iron asymmetrically coordinated with both nitrogen and sulfur, dispersed on hierarchically porous carbon (FeSA‐NS/C). The newly‐developed FeSA‐NS/C catalyst exhibited a high catalytic activity and selectivity for oxygen reduction to produce H2O2 at a high current of 100 mA cm−2 with a record high H2O2 selectivity of 90 %. An accumulated H2O2 concentration of 5.8 wt.% is obtained for the electrocatalysis process, which is sufficient for medical disinfection. Combined theoretical calculations and experimental characterizations verified the rationally‐designed catalytic active center with the atomic Fe site stabilized by three‐coordinated nitrogen atoms and one‐sulfur atom (Fe‐N3S‐C). It was further found that the replacement of one N atom with S atom in the classical Fe‐N4‐C active center could induce an asymmetric charge distribution over N atoms surrounding the Fe reactive center to accelerate proton spillover for a rapid formation of the OOH* intermediate, thus speeding up the whole reaction kinetics of oxygen reduction for H2O2 electrosynthesis.

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Electrochemical oxygen evolution reaction (OER) kinetics are heavily correlated with hybridization of the transition metal d‐orbital and oxygen intermediate p‐orbital, which dictates the barriers of intermediate adsorption/desorption on the active sites of catalysts. Herein, w e develop a strategy involving strain engineering and coordination regulation to enhance the hybridization of Ni 3d and O 2p orbitals, and the as‐synthesized Ni‐2,6‐naphthalenedicarboxylic acid metal‐organic framework (DD‐Ni‐NDA) nanosheets delivered a low OER overpotential of 260 mV to reach 10 mA cm−2. By integrating an alkaline anion exchange membrane electrolyzer and Pt/C electrode, 200 and 500 mA cm−2 current densities w ere reached with cell voltages of 1.6 and 2.1 V, respectively. When loaded on BiVO4 photoanode, the nanosheet enables highly active solar‐driven water oxygen. Structural characterizations together with theoretical calculations reveal that the spin state of centre Ni atoms is regulated by tensile strain and unsaturated coordination defects in DD‐Ni‐NDA, and such spin regulation facilitates spin‐dependent charge transfer of the OER. Molecular orbital hybridization analysis reveals the mechanism of OH* and OOH* adsorption energy regulation by changes in DD‐Ni‐NDA spin state, which provides a deeper understanding of the electronic structure design of catalysts for the OER.This article is protected by copyright. All rights reserved